EP1323759B1 - Revêtement sous forme de poudre contenant une résine époxyde durcissable à basse température - Google Patents

Revêtement sous forme de poudre contenant une résine époxyde durcissable à basse température Download PDF

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Publication number
EP1323759B1
EP1323759B1 EP02102833A EP02102833A EP1323759B1 EP 1323759 B1 EP1323759 B1 EP 1323759B1 EP 02102833 A EP02102833 A EP 02102833A EP 02102833 A EP02102833 A EP 02102833A EP 1323759 B1 EP1323759 B1 EP 1323759B1
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EP
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Prior art keywords
epoxy resin
powder coating
weight
coating composition
parts
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02102833A
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German (de)
English (en)
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EP1323759A1 (fr
Inventor
Chongsoo Park
Youngsoo Park
Jinwoo Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kukdo Chemical Co Ltd
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Kukdo Chemical Co Ltd
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Priority claimed from KR1020020064617A external-priority patent/KR100546716B1/ko
Application filed by Kukdo Chemical Co Ltd filed Critical Kukdo Chemical Co Ltd
Publication of EP1323759A1 publication Critical patent/EP1323759A1/fr
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Publication of EP1323759B1 publication Critical patent/EP1323759B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates to a powder coating composition containing a low temperature curable epoxy resin, and more particularly to a powder coating composition containing a low temperature curable epoxy resin, which can be readily cured at a low temperature, thereby capable of being applied to coating objects that are difficult in elevating temperature, or are thermally sensitive.
  • Epoxy resin is a molecule having two or more epoxy functional groups.
  • Epoxy resin is a kind of thermosetting resin irreversibly crosslinked to form a three-dimensional structure at room temperature or under the influence of heat.
  • epoxy resins are different from other thermosetting resins in that curing is not carried out on heating in the absence of a catalyst or a curing agent.
  • An epoxy resin is widely used in molded products, cast products, coatings and the like due to its excellent adhesion, mechanical property, electrical property, chemical resistance, etc.
  • the epoxy resin is excellent in adhesion, water resistance, and chemical resistance to various types of coating objects, including metals. Accordingly, the epoxy resin based coatings are widely used instead of alkyd resin or phenolic resin based coatings.
  • a powder coating composition is a coating film forming composition in the form of powder and does not use a volatile solvent such as an organic solvent or water.
  • the powder coating composition is applied to a coating object and then heat-melted.
  • the powder coating composition has advantages in that it does not use a solvent, can form a thick coating film with just one coating, and can use a high molecular weight resin which is not dissolved in a solvent, compared with a solvent-type coating composition. Accordingly, use and demand for the powder coating composition are increasing in fields of construction materials, automobile parts, pipes, mechanical parts, electronic products, iron furniture and the like.
  • the powder coating composition is generally produced as follows: a resin for a powder coating composition, a curing agent, a pigment and an additive, and the like are mixed in a blender. The mixture is placed into an extruder or a roll-mill, where it is heated at a temperature in a range of 80 to 130°C, melt-mixed and ground into a powder. Thereafter, a coating object is coated with the ground powder coating composition.
  • the powder coating composition can be produced by mixing the above components in a mixer such as a ball-mill or a ribbon blender at room temperature.
  • the powder coating composition can be coated by various coating techniques, for example, a spray coating technique, a flow coating technique or an electrostatic coating technique.
  • the electrostatic coating technique is most widely used.
  • the resin for the powder coating composition examples are an epoxy resin and a polyester resin.
  • the epoxy resin is generally a bisphenol-A epoxy resin manufactured by reacting bisphenol-A and epichlorohydrin in the presence of a base or an acid.
  • the bisphenol-A epoxy resin is excellent in chemical resistance and corrosion resistance. However, because it is cured at a high temperature, for thick metallic coating objects that cannot reach an elevated temperature within a short time, a large amount of heat energy must be applied thereto, and thus energy use increases. Further, it is difficult to apply to coating objects that are thermally sensitive.
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a powder coating composition containing a low temperature curable epoxy resin with corrosion resistance.
  • a powder coating composition comprising :
  • the epoxy resin is represented by Formula 4 below: wherein R 1 , R 2 and n are as described above.
  • R 1 and R 2 each are individually a hydrogen or a methyl group, and n is a real number of 1 to 15 ; n may also be an integer of 1 to 15.
  • the curing agent is preferably a phenolic curing agent such as a bisphenol-A curing agent or a polyester-based curing agent.
  • the powder coating composition preferably further comprises 10 to 200 parts by weight of a universal bisphenol-A epoxy resin for powder coating compositions (epoxy equivalent weight: 600 to 1500 g/eq) per 100 parts by weight of the low temperature curable epoxy resin of the Formula 1.
  • the powder coating composition preferably further comprises one or more components selected from the group consisting of a pigment, an antioxidant, a filler, a light stabilizer, a curing promoter and an ultraviolet absorber.
  • alkyl group having from 1 to 5 carbon atoms examples include methyl, ethyl, propyl, butyl groups, etc.
  • n is a number of from 0.1 to 30, and preferably from 1 to 15.
  • X is a hydrogen atom or a glycidyl group. More than 20% of X are glycidyl groups, and preferably more than 25% are glycidyl groups.
  • n and X refer to average values.
  • n is less than 0.1, or less than 20% of X are glycidyl groups in the epoxy resin, the content of multifunctional epoxy compounds not less than trifunctional is low and thus the epoxy resin is unsatisfactory in its curability and properties of the coated object.
  • a conventional epoxy resin is excellent in corrosion resistance but is generally cured at a high temperature.
  • the low temperature curable epoxy resin of the formula 1 with multifunctional groups was used in the powder coating composition of the present invention.
  • the epoxy resin of the present invention not only maintains corrosion resistance, but can also be cured at a low temperature.
  • the powder coating composition of the present invention comprises the multifunctional and low temperature curable epoxy resin of the Formula 1 as its subject, and a bisphenol-A resin or a polyester resin as a curing agent.
  • a bisphenol-A resin or a polyester resin is used instead of a conventional coating curing agent such as an acid anhydride or amine, is to cure the powder coating composition at a low temperature.
  • the amount of the bisphenol-A curing agent or the polyester curing agent to be used in the powder coating composition of the present invention is 30 to 500 parts by weight per 100 parts by weight of the multifunctional epoxy resin of the Formula 1. This is to ensure the functional groups of the multifunctional epoxy resin completely react one-to-one with those of the curing agent, so as not to leave any epoxy resin functional groups unreacted.
  • the epoxy resin of Formula 1 contained in the powder coating composition according to the present invention preferably has an epoxy equivalent weight of 200 ⁇ 600g/eq. When the epoxy equivalent weight exceeds 600g/eq, there are risks of coloring of cured material and poor physical properties.
  • a polyester curing agent to be used in the powder coating composition of the present invention is that conventionally used in powder coating compositions in the pertinent art.
  • the polyester curing agent is not particularly limited provided that it has carboxyl groups capable of participating in the curing reaction with the epoxy resin of the present invention.
  • the polyester curing agent has preferably a glass transition temperature of 55 to 65°C and an acid value of 30 to 80.
  • polyester curing agent examples include trademark KP-3520 (KUKDO CHEMICAL Co., LTD, Korea), trademark KP-3531 (KUKDO CHEMICAL Co., LTD, Korea), trademark KP-3620 (KUKDO CHEMICAL Co., LTD, Korea), trademark KP-3720 (KUKDO CHEMICAL Co., LTD, Korea), and the like.
  • a bisphenol-A curing agent to be used in the powder coating composition of the present invention is that conventionally used in powder coating compositions in the pertinent art.
  • the bisphenol-A curing agent has OH terminal groups and the equivalent weight of the OH groups is preferably 200 to 800.
  • Examples of the bisphenol-A curing agent commercially available are trademark KD-410J (KUKDO CHEMICAL Co., LTD, Korea), trademark KD-406 (KUKDO CHEMICAL Co., LTD, Korea), trademark KD-420 (KUKDO CHEMICAL Co., LTD, Korea), trademark KD-426 (KUKDO CHEMICAL Co., LTD, Korea), and the like.
  • the powder coating composition further comprises a universal bisphenol-A epoxy resin for powder coating compositions with an epoxy equivalent weight of 600 to 1500 g/eq.
  • the universal bisphenol-A epoxy resin reacts with the bisphenol-A curing agent or the polyester curing agent upon the curing of the powder coating composition of the present invention.
  • the universal bisphenol-A epoxy resin for powder coating compositions with an epoxy equivalent weight of 600 to 1500g/eq is preferably added in an amount of 10 to 200 parts by weight per 100 parts by weight of the low temperature epoxy resin of the Formula 1. If the added amount is less than 10 parts by weight, little effect is obtained, while if it exceeds 200 parts by weight, low temperature curability is lost and mechanical properties deteriorate.
  • the powder coating composition of the present invention preferably comprises a desired amount of a defoaming agent known in the pertinent art.
  • the defoaming agent serves to control foams formed in the surface of a coating film.
  • the content thereof is preferably 0.1 to 20 parts by weight based on the total weight of the composition. If the content is outside the above range, physical properties are adversely affected.
  • the leveling agent used in the powder coating composition imparts smoothness to a coating film. Its content is preferably 0.1 to 20 parts by weight. If the content is outside the above range, physical properties are adversely affected.
  • the powder coating composition can further comprise known additives conventionally added to powder coating compositions in the pertinent art.
  • the additives are a pigment, an antioxidant, a filler, a light stabilizer, a curing promoter or an ultraviolet absorber, or the like.
  • the multifunctional low temperature curable epoxy resin of the Formula 1 used in the present invention can be prepared by polymerizing a bisphenol-A epoxy resin of Formula 2 below, and an epichlorohydrin.
  • the epichlorohydrin used to prepare the low temperature curable epoxy resin of the present invention is also referred to as 1,2-epoxy-3-chloropropane. It has the chemical structure of Formula 3 below and is a colorless liquid.
  • a DL-epichlorohydrin and a L-epichlorohydrin are known.
  • the DL-epichlorohydrin is common.
  • the multifunctional epoxy resin of the formula 1 of the present invention can be prepared by reacting the bisphenol-A epoxy resin of the Formula 2 and the epichlorohydrin of the Formula 3.
  • the preparation method thereof is as illustrated in Equation 1 below.
  • the multifunctional epoxy resin of the formula 1 can be obtained by reacting the bisphenol-A epoxy resin of the Formula 2 and an excess of the epichlorohydrin of the Formula 3 in the presence of a catalyst.
  • the reaction is carried out in a range of 50 to 180°C and under reduced pressure of 30 to 250 torr (3999.66 Pa to 33330.50 Pa).
  • the reaction time is 2 to 30 hours.
  • alkali compounds examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.
  • Lewis acids examples include boron trifluoride, tin chloride, zinc chloride, etc.
  • phase-transfer catalysts examples include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, N,N-dimethylpyrrolidium chloride, N-ethyl-N-methylpyrrolidium iodide, N-butyl-N-methylpyrrolidium bromide, N-benzyl-N-methylpyrrolidium chloride, N-ethyl-N-methylpyrrolidium bromide, N-butyl-N-methylmorphonium bromide, N-butyl-N-methylmorphonium iodide, N-allyl-N-methylmorphonium bromide, N-methyl-N-benzylpiperidium chloride, N-methyl-N-benzylpiperidium bromide, N,N-dimethylpiperidium iodide, N-methyl-N-ethylpiperid
  • the amount of epichlorohydrin used in the reaction is not less than 1 equivalent weight, and preferably within the range of 2 ⁇ 10 equivalent weight, relative to 1 equivalent weight of hydroxyl group of diglycidyl ether.
  • the amount of the alkali compounds used in the reaction is within the range of 0.1 ⁇ 2.0 moles, and preferably 0.3 ⁇ 1.5 moles, relative to 1 equivalent weight of glycidylated hydroxyl group.
  • the amount of the phase-transfer catalysts used is within the range of 0.01 ⁇ 10 mol%, and preferably 0.2 ⁇ 2 mol%, based on the total weight of the reactants.
  • the reaction can be carried out in a solvent such as a hydrocarbon, ether or ketone, and an excess of epichlorohydrin can be used as a solvent.
  • a solvent such as a hydrocarbon, ether or ketone
  • the content of the glycidyl group can be appropriately adjusted depending on various factors such as the amount of epichlorohydrin used, reaction temperature, reaction pressure, reaction time, and types and amount of catalysts used.
  • the multifunctional epoxy resin of the Formula 1 obtained in above reaction has an epoxy equivalent weight of 200 to 600 and an n value of 1 to 30.
  • the epichlorohydrin of the Formula 3 is preferably added in an excess amount relative to the bisphenol-A epoxy resin of the Formula 2.
  • the molar ratio of the bisphenol-A epoxy to the epichlorohydrin is 1:30 to 1:80.
  • the bisphenol-A epoxy resin of the Formula 2 has preferably an epoxy equivalent weight of 400 to 2000, and more preferably an epoxy equivalent weight of 400 to 1000.
  • the bisphenol-A epoxy resin of the Formula 2 can be selected among products commercially available, without being particularly limited.
  • the bisphenol-A epoxy resin of the Formula 2 can also be prepared according to Equation 2 below. wherein R 1 , R 2 and n are as defined in the Formula 1.
  • the conventional bisphenol-A and the epichlorohydrin of the Formula 3 can react to form the bisphenol-A epoxy resin of the Formula 2.
  • each mixture was passed through the extruder ZSK25 (W&P, Main screw rpm: 250).
  • the extruded mixtures were ground and applied onto the surface of metal using a GEMA electrostatic spray gun (60-80KV).
  • the metal was cured at 140°C.
  • a powder coating composition having the composition shown in Table 1 below was prepared in the same manner as described in the Example 1.
  • Table 1 Components Examples Comp. Example 1 2 3 4 5 6 7 8 9 10 11 12 Multifunctional epoxy resin (EP-1) 90 69 Multifunctional epoxy resin (EP-2) 65 Multifunctional epoxy resin (EP-3) 78 Multifunctional epoxy resin (EP-4) 77 59 Multifunctional epoxy resin (EP-5) 81 57 Multifunctional epoxy resin (EP-6) 83 Multifunctional epoxy resin (EP-7) Bisphenol-A epoxy resin of Formula 4 29 28 33 32 38 35 95 64 49 KD-242G 43 67 140 KP-3520 210 202 207 188 223 210 219 206 182 205 193 184 160 Benzoin 5 5 5 5 5 5 5 5 5 5 5 5 5 5 PV5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 BaSO 4 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 TiO 2 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150
  • the trademark KD-242G (made by KUKDO CHEMICAL Co., LTD) is a universal bisphenol-A epoxy resin for powder coating compositions with an epoxy equivalent weight of 650-725 g/eq
  • the trademark KP-3520 (made by KUKDO CHEMICAL Co., LTD) is a polyester resin for a powder coating composition as a curing agent.
  • the benzoin and the trademark PV5 (made by Wolee) were used as a defoaming agent and a leveling agent, respectively.
  • the powder coating composition comprising the multifunctional and low temperature curable epoxy resin of the present invention has excellent curability at a low temperature, thereby capable of being applied to thick metallic coating objects that cannot reach an elevated temperature within a short time, or coating objects that are thermally sensitive. Accordingly, the present invention is advantageous in terms of energy savings and environmental protection, because sufficient curing can be accomplished with a small amount of energy.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

Claims (7)

  1. - Composition de revêtement pulvérulent, comprenant :
    - 100 parties en poids d'une résine époxy durcissable à basse température, représentée par la Formule 1 ci-dessous :
    Figure imgb0011
     dans laquelle :
    - n est un nombre réel de 0,1 à 30;
    - R1 et R2 sont indépendamment un hydrogène ou un groupe alkyl ou alcoxy non substitué ou substitué, ayant de 1 à 5 atomes de carbone ; et
    - X est un atome d'hydrogène ou un groupe glycidyle, dans lequel plus de 20% de X sont des groupes glycidyle ; et
    - 30 à 500 parties en poids d'un agent de durcissement.
  2. - Composition de revêtement pulvérulent selon la revendication 1, dans laquelle la résine époxy est représentée par la Formule 4 ci-dessous :
    Figure imgb0012
     dans laquelle R1, R2 et n sont tels que définis à la revendication 1.
  3. - Composition de revêtement pulvérulent selon l'une des revendications 1 et 2, dans laquelle R1 et R2 sont tous deux méthyle et n est un nombre réel de 1 à 15.
  4. - Composition de revêtement pulvérulent selon l'une quelconque des revendications 1 à 3, qui comprend 0,1 à 20 parties en poids d'un agent antimousse et 0,1 à 20 parties en poids d'un agent d'unisson.
  5. - Composition de revêtement pulvérulent selon l'une quelconque des revendications 1 à 4, dans laquelle l'agent de durcissement est un agent de durcissement phénolique ou un agent de durcissement à base de polyester.
  6. - Composition de revêtement pulvérulent selon l'une quelconque des revendications 1 à 5, qui comprend 10 à 200 parties en poids d'une résine bisphénol A époxy universelle pour revêtements pulvérulents ayant un poids équivalent en époxy de 600 à 1500 g/éq, sur la base de 100 parties en poids de la résine époxy durcissable à basse température représentée par la Formule 1.
  7. - Composition de revêtement pulvérulent selon l'une quelconque des revendications 1 à 6, qui comprend en outre au moins un additif choisi dans le groupe constitué par un pigment, un anti-oxydant, une charge, un stabilisant vis-à-vis de la lumière, un promoteur de durcissement et un agent absorbant le rayonnement ultraviolet.
EP02102833A 2001-12-19 2002-12-19 Revêtement sous forme de poudre contenant une résine époxyde durcissable à basse température Expired - Lifetime EP1323759B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20010081150 2001-12-19
KR2001081150 2001-12-19
KR1020020064617A KR100546716B1 (ko) 2001-12-19 2002-10-22 저온 경화성 에폭시 수지를 이용한 분체도료용 조성물
KR2002064617 2002-10-22

Publications (2)

Publication Number Publication Date
EP1323759A1 EP1323759A1 (fr) 2003-07-02
EP1323759B1 true EP1323759B1 (fr) 2007-03-07

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EP02102833A Expired - Lifetime EP1323759B1 (fr) 2001-12-19 2002-12-19 Revêtement sous forme de poudre contenant une résine époxyde durcissable à basse température

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EP (1) EP1323759B1 (fr)
CN (1) CN1244646C (fr)
AT (1) ATE356159T1 (fr)
DE (1) DE60218619T2 (fr)
ES (1) ES2282372T3 (fr)
TW (1) TWI247029B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864057B (zh) * 2010-05-10 2012-05-09 宏昌电子材料股份有限公司 粉末涂料用环氧树脂及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623701A (en) * 1985-07-10 1986-11-18 The Dow Chemical Company Multifunctional epoxy resins
US4952647A (en) * 1988-10-14 1990-08-28 The Dow Chemical Company Aliphatic, non-hydrolyzable chloride-containing epoxy resins and process for their production
US5218061A (en) * 1990-09-17 1993-06-08 Nippon Kayaku Kabushiki Kaisha Partially post-glycidylated epoxy resin, epoxy resin composition and cured product thereof
JP3281473B2 (ja) * 1994-01-17 2002-05-13 日本化薬株式会社 フレキシブルプリント配線板用レジストインキ組成物及びその硬化物
US6218482B1 (en) * 1994-02-24 2001-04-17 New Japan Chemical Co., Ltd. Epoxy resin, process for preparing the resin and photo-curable resin composition and resin composition for powder coatings containing the epoxy resin

Also Published As

Publication number Publication date
CN1244646C (zh) 2006-03-08
ES2282372T3 (es) 2007-10-16
TWI247029B (en) 2006-01-11
CN1427051A (zh) 2003-07-02
DE60218619D1 (de) 2007-04-19
TW200406470A (en) 2004-05-01
EP1323759A1 (fr) 2003-07-02
ATE356159T1 (de) 2007-03-15
DE60218619T2 (de) 2007-11-29

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